US4873336A - Process for the preparation of N-vinyl lactams - Google Patents

Process for the preparation of N-vinyl lactams Download PDF

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Publication number
US4873336A
US4873336A US07/183,559 US18355988A US4873336A US 4873336 A US4873336 A US 4873336A US 18355988 A US18355988 A US 18355988A US 4873336 A US4873336 A US 4873336A
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psig
product
pyrrolidone
acetylene
catalyst
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US07/183,559
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Kou-Chang Liu
Paul D. Taylor
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ISP Investments LLC
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GAF Corp
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Assigned to GAF CORPORATION, A CORP. OF DE. reassignment GAF CORPORATION, A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: LIU, KOU-CHANG, TAYLOR, PAUL D.
Priority to PCT/US1989/000827 priority patent/WO1989009210A1/en
Priority to EP19890904992 priority patent/EP0408652A4/en
Priority to AU34431/89A priority patent/AU3443189A/en
Priority to JP1504669A priority patent/JPH04501252A/en
Assigned to CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATION reassignment CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DORSET INC. A CORP OF DELAWARE
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Assigned to GAF CHEMICALS CORPORATION reassignment GAF CHEMICALS CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 04/11/1989 Assignors: DORSET INC.
Priority to KR1019890702195A priority patent/KR900700451A/en
Assigned to DORSET INC., A DE CORP. reassignment DORSET INC., A DE CORP. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 10, 1989 Assignors: GAF CORPORATION, A DE CORP.
Assigned to CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE reassignment CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GAF CHEMICALS CORPORATION, A CORP. OF DE
Assigned to ISP INVESTMENTS INC. reassignment ISP INVESTMENTS INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 06/06/1991 Assignors: ISP 3 CORP.
Assigned to ISP 3 CORP reassignment ISP 3 CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GAF CHEMICALS CORPORATION
Assigned to GAF CHEMICALS CORPORATION, SUTTON LABORATORIES, INC., GAF BUILDING MATERIALS CORPORATION reassignment GAF CHEMICALS CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION)
Assigned to BANKERS TRUST COMPANY reassignment BANKERS TRUST COMPANY SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CABOT SAFETY INTERMEDIATE CORPORATION
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom

Definitions

  • Prior processes for the preparation of vinyl lactams are generally carried out in two-stages where, in the first stage, potassium hydroxide is reacted with the lactam to produce the corresponding lactam salt catalyst and water followed by vinylation of lactam with acetylene in the presence of the salt catalyst in the second stage to produce the desired vinylated product.
  • This process is hampered by the formation of potassium 4-aminobutyrate by-product caused by lactam ring opening unless great care is taken to prevent its formation by removal of water during the reaction and by employing a sterically hindered alkoxide so as to prevent ring opening. Ring opening destroys the catalyst and the process looses catalytic activity; thus for all intents and purposes this should be avoided.
  • Another object of the invention is to produce a vinylpyrrolidone containing essentially no metal amino butyrate by-product.
  • Another object is to prevent catalyst ring opening and consequent loss of reaction activity.
  • Still another object is to eliminate costly removal of water in the preparation of a catalyst for synthesis of N-vinyl lactams.
  • a non-aqueous liquid phase process for the preparation of an N-vinyl lactam which is effected in a single stage reaction.
  • the reaction comprises contacting with acetylene under between about 25 and about 125 psig. acetylene partial pressure preferably in the presence of an inert gas diluent and a catalyst having the formula ##STR4## wherein each of R 1 , R 2 and R 3 are alkyl groups of from 1 to 4 carbon atoms or aryl or one of R 1 , R 2 and R 3 is hydrogen and M is an alkali metal, preferably a metal selected from the group of potassium, sodium and lithium.
  • an acetylene diluent can be employed at a concentration of between about 25 and about 200 wt. % of the total reaction mixture.
  • the diluent when used, can be selected from any one of the inert gases such as nitrogen, helium, argon, krvoton, methane, ethane, propane, or mixtures thereof.
  • the lactam reactants of this invention are those having the formula ##STR5## wherein n has a value of from 1 to 3 and can be branched or linear. Of these, 2-pyrrolidone and caprolactam are preferred and 2-pyrrolidone is most preferred.
  • the catalysts of the present invention wherein R 1 , R 2 and R 3 represent methyl or ethyl groups and M is potassium or sodium are most effective. Of this group, potassium t-butoxide is conveniently useful.
  • the catalyst is employed in a molar ratio of from about 1:20 to about 1:200, more desirably from 1:60 to 1:100, based on lactam.
  • the reaction is generally effected at a temperature between about 125° C. and 185° C. for a period of from about 2 to about 20 hours, preferably at a temperature of from about 135° C. to about 165° C. for a period of about 5 to 15 hours.
  • the system is pressurized with between about 70 and about 110 psig. of acetylene and between about 25 and about 200 psig. of inert gas diluent. More often the inert gas is employed at a partial pressure of from about 60 to about 125 psig.
  • a main advantage of the present process is that a sterically hindered alkanol is produced instead of the water generated during catalyst preparation. Sterically hindered tertiary and secondary alkanols cause no ring opening of the lactam reactant, thus obviating the need for a tedious and separate catalyst preparation step in the process.
  • the product of the process can be produced in yields above 90% if desired depending upon the pressure employed and the reaction time.
  • 2-pyrrolidone (628 g., 7.47 moles) was charged into a 1 liter four neck round bottom flask equipped with a condenser, mechanical stirrer, thermometer and nitrogen inlet, and heated to 90° C.
  • Potassium hydroxide (7.4 g., 85% pellet, 0.11 moles) was added.
  • the solution was held at 90° C. and 0.1 mm Hg pressure for 1 hour to remove water from the solution.
  • This solution was then transferred into a 1 liter stainless steel autoclave and vinylated with acetylene under the same conditions of temperature and pressure as employed in Example 1. After 8 hours of reaction, 75% conversion with 90% selectivity to N-vinyl pyrrolidone was obtained.
  • Example 1 it will become apparent from the accompanying description and disclosure that many alterations and variations can be made in Examples 1 and 5 without departing from the scope of the invention.
  • any of the t-alkyl metal salt catalysts described herein can be substituted for potassium t-butoxide to provide the same advantages over the reactions set forth in Examples 2 and 3.
  • other diluents such as propane/ethane, or other aforementioned inert gases or mixtures thereof can be substituted for nitrogen or propane to provide the same beneficial effects.
  • the reaction in Example 1 can be carried out in a continuous process with recycle of unreacted material, if desired.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrrole Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)

Abstract

The invention relates to the preparation of N-vinyl lactams having the formula ##STR1## wherein n is an integer having an value of from 1 to 3 in a one-stage, non-aqueous process which comprises reacting a lactam having the formula ##STR2## with acetylene under an acetylene partial pressure of from about 25 to about 125 psig. in the presence of an inert gas diluent and a catalyst having the formula ##STR3## wherein R1, R2 and R3 are all lower alkyl or alyl or one of R1, R2 and R3 can also be hydrogen and M is a metal selected from the group of cesium, potassium, sodium and lithium.

Description

BACKGROUND OF THE INVENTION
Prior processes for the preparation of vinyl lactams are generally carried out in two-stages where, in the first stage, potassium hydroxide is reacted with the lactam to produce the corresponding lactam salt catalyst and water followed by vinylation of lactam with acetylene in the presence of the salt catalyst in the second stage to produce the desired vinylated product. This process is hampered by the formation of potassium 4-aminobutyrate by-product caused by lactam ring opening unless great care is taken to prevent its formation by removal of water during the reaction and by employing a sterically hindered alkoxide so as to prevent ring opening. Ring opening destroys the catalyst and the process looses catalytic activity; thus for all intents and purposes this should be avoided.
Accordingly, it is an object of the present invention to obviate the above difficulty by a commercially feasible and economical process.
Another object of the invention is to produce a vinylpyrrolidone containing essentially no metal amino butyrate by-product.
Another object is to prevent catalyst ring opening and consequent loss of reaction activity.
Still another object is to eliminate costly removal of water in the preparation of a catalyst for synthesis of N-vinyl lactams.
These and other objects of the invention will become apparent from the following description and disclosure.
THE INVENTION
According to this invention there is provided a non-aqueous liquid phase process for the preparation of an N-vinyl lactam which is effected in a single stage reaction. The reaction comprises contacting with acetylene under between about 25 and about 125 psig. acetylene partial pressure preferably in the presence of an inert gas diluent and a catalyst having the formula ##STR4## wherein each of R1, R2 and R3 are alkyl groups of from 1 to 4 carbon atoms or aryl or one of R1, R2 and R3 is hydrogen and M is an alkali metal, preferably a metal selected from the group of potassium, sodium and lithium.
If desired, an acetylene diluent can be employed at a concentration of between about 25 and about 200 wt. % of the total reaction mixture. The diluent, when used, can be selected from any one of the inert gases such as nitrogen, helium, argon, krvoton, methane, ethane, propane, or mixtures thereof.
The lactam reactants of this invention are those having the formula ##STR5## wherein n has a value of from 1 to 3 and can be branched or linear. Of these, 2-pyrrolidone and caprolactam are preferred and 2-pyrrolidone is most preferred. The catalysts of the present invention wherein R1, R2 and R3 represent methyl or ethyl groups and M is potassium or sodium are most effective. Of this group, potassium t-butoxide is conveniently useful. The catalyst is employed in a molar ratio of from about 1:20 to about 1:200, more desirably from 1:60 to 1:100, based on lactam.
The reaction is generally effected at a temperature between about 125° C. and 185° C. for a period of from about 2 to about 20 hours, preferably at a temperature of from about 135° C. to about 165° C. for a period of about 5 to 15 hours. Under optimum conditions, the system is pressurized with between about 70 and about 110 psig. of acetylene and between about 25 and about 200 psig. of inert gas diluent. More often the inert gas is employed at a partial pressure of from about 60 to about 125 psig.
A main advantage of the present process is that a sterically hindered alkanol is produced instead of the water generated during catalyst preparation. Sterically hindered tertiary and secondary alkanols cause no ring opening of the lactam reactant, thus obviating the need for a tedious and separate catalyst preparation step in the process.
The product of the process can be produced in yields above 90% if desired depending upon the pressure employed and the reaction time.
Having generally described the invention, reference is now had to the accompanying Examples of which Examples 1 and 4 illustrate preferred embodiments of the invention and Examples 2 and 3 are presented for comparative purposes. These Examples should in no way be construed as limiting to the scope of the invention as more broadly described above and in the appended claims.
EXAMPLE 1
Into a 1 liter stainless steel autoclave was charged 628 g. (7.4 moles) of 2-pyrrolidone and 12.6 g. (0.11 mole) of potassium t-butoxide. The autoclave was purged three times with nitrogen at room temperature and then heated to 160° C. Acetylene (partial pressure 100 psig.) was added and the solution was agitated at a speed of 1800 rpm. After 8 hours of vinylation, a 62% conversion with 90% selectivity to N-vinyl pyrrolidone was obtained.
EXAMPLE 2
Into a 1 liter stainless steel autoclave was charged 628 g. (7.4 moles) of 2-pyrrolidone and 7.4 g., 0.11 moles of 85% potassium hydroxide pellets. This mixture was vinylated with acetylene under the same conditions of temperature and pressure as employed in Example 1. After 8 hours of reaction, less than 5% of N-vinyl pyrrolidone was obtained.
EXAMPLE 3
Into a 1 liter stainless steel autoclave was charged 628 g. (7.4 moles) of 2-pyrrolidone and 12.6 g. (0.11 mole) of potassium t-butoxide. The autoclave was purged three times with nitrogen at room temperature after which 100 pounds of nitrogen was added, the temperature was raised to 160° C. and the pressure of nitrogen was adjusted to 100 psig. and acetylene (100 psig) was added. The solution is agitated at a speed of 1800 rpm. After 8 hours of vinylation, about 50% yield of N-vinyl pyrrolidone was obtained.
EXAMPLE 4
2-pyrrolidone (628 g., 7.47 moles) was charged into a 1 liter four neck round bottom flask equipped with a condenser, mechanical stirrer, thermometer and nitrogen inlet, and heated to 90° C. Potassium hydroxide (7.4 g., 85% pellet, 0.11 moles) was added. The solution was held at 90° C. and 0.1 mm Hg pressure for 1 hour to remove water from the solution. This solution was then transferred into a 1 liter stainless steel autoclave and vinylated with acetylene under the same conditions of temperature and pressure as employed in Example 1. After 8 hours of reaction, 75% conversion with 90% selectivity to N-vinyl pyrrolidone was obtained.
EXAMPLE 5 Continuous Process
Into a nitrogen purged 1 liter stainless steel sealed reactor is charged 628 g. of 2-pyrrolidone and 12 g. of sodium t-butoxide catalyst. The reactor is then heated to 150° C. and acetylene was added to obtain a partial pressure of 100 psig. Also propane is charged to a partial pressure of 100 psig. The resulting liquid mixture is agitated at 150° C. until about 50% conversion of 2-pyrrolidone to N-vinyl pyrrolidone product takes place. The product mixture is then withdrawn and product and unreacted 2-pyrrolidones are separated by fractional distillation. The N-vinyl-2-pyrrolidone substantially free of contamination is recovered as the product of the process and the 2-pyrrolidone is recycled to the reactor for contact with additional catalyst and acetylene feed.
It will become apparent from the accompanying description and disclosure that many alterations and variations can be made in Examples 1 and 5 without departing from the scope of the invention. For example, any of the t-alkyl metal salt catalysts described herein can be substituted for potassium t-butoxide to provide the same advantages over the reactions set forth in Examples 2 and 3. Also, other diluents such as propane/ethane, or other aforementioned inert gases or mixtures thereof can be substituted for nitrogen or propane to provide the same beneficial effects. Still further, the reaction in Example 1 can be carried out in a continuous process with recycle of unreacted material, if desired.

Claims (16)

Having thus described the invention, what is claimed is:
1. A single stage non-aqueous liquid process for the preparation of an N-vinyl lactam which comprises reacting a lactam having the formula ##STR6## wherein n is an integer having a value of from 1 to 3 with acetylene under an acetylene partial pressure of from about 25 to about 125 psig. in the presence of a catalyst having the formula ##STR7## wherein R1, R2 and R3 are each lower alkyl or aryl or wherein one of R1, R2 and R3 is hydrogen and M is an alkali metal.
2. The process of claim 1 wherein said lactam is 2-pyrrolidone and said product is N-vinyl-2-pyrrolidone.
3. The process of claim 1 wherein said lactam is caprolactam and said product is N-vinyl-caprolactam.
4. The process of claim 1 wherein said process is effected in the presence of an inert gas diluent and said inert gas diluent is selected from the group of nitrogen, helium, argon, krypton, propane, ethane and methane and is employed in an amount of from about 25 wt. % to about 200 wt. % of the total reaction mixture.
5. The product of claim 4 wherein said inert gas diluent is employed at a partial pressure of from about 60 psig. to about 125 psig.
6. The process of claim 4 wherein said diluent is nitrogen.
7. The process of claim 4 wherein said diluent is propane.
8. The process of claim 2 wherein M is a metal selected from the group of potassium, sodium, lithium and cesium.
9. The process of claim 8 wherein said catalyst is potassium t-butoxide.
10. The process of claim 8 wherein said catalyst is sodium t-butoxide.
11. The process of claim 1 wherein said process is effected at a temperature of between about 125° C. and about 185° C.
12. The process of claim 11 wherein the process is carried out with agitation over a period of from about 3 to about 20 hours.
13. The process of claim 2 wherein said process is effected at a temperature of between about 135° C. and 165° C. for a period of from about 5 to about 15 hours.
14. The process of claim 2 wherein the partial pressure of acetylene is between about 70 psig. and about 110 psig.
15. The process of claim 14 wherein the reaction is continued until between about 40 wt. % and about 65 wt. % of product is obtained.
16. The process of claim 15 wherein the N-vinyl pyrrolidone product and unreacted pyrrolidone are separated from the product mixture by fractional distillation and the unreacted pyrrolidone is recycled to the reaction for contact with an additional amount of catalyst and acetylene.
US07/183,559 1988-03-28 1988-03-28 Process for the preparation of N-vinyl lactams Expired - Fee Related US4873336A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US07/183,559 US4873336A (en) 1988-03-28 1988-03-28 Process for the preparation of N-vinyl lactams
PCT/US1989/000827 WO1989009210A1 (en) 1988-03-28 1989-03-02 Process for the preparation of n-vinyl lactams
EP19890904992 EP0408652A4 (en) 1988-03-28 1989-03-02 Process for the preparation of n-vinyl lactams
AU34431/89A AU3443189A (en) 1988-03-28 1989-03-02 Process for the preparation of n-vinyl lactams
JP1504669A JPH04501252A (en) 1988-03-28 1989-03-02 Method for producing N-vinyl lactam
KR1019890702195A KR900700451A (en) 1988-03-28 1989-11-27 Manufacturing method of N-vinyl lactam

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EP (1) EP0408652A4 (en)
JP (1) JPH04501252A (en)
KR (1) KR900700451A (en)
AU (1) AU3443189A (en)
WO (1) WO1989009210A1 (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5329021A (en) * 1993-02-04 1994-07-12 Isp Investments Inc. Process for the production of pure vinyl pyrrolidone
US5665889A (en) * 1996-01-22 1997-09-09 Industrial Technology Research Institute Method for the production of N-vinyl-2-pyrrolidone by vinylation
US5670639A (en) * 1995-03-15 1997-09-23 Basf Aktiengesellschaft Preparation of n-vinyllactams
US5710284A (en) * 1995-10-02 1998-01-20 Basf Aktiengesellschaft Purification of N-vinylpyrrolidone by crystallization
US5945544A (en) * 1997-04-09 1999-08-31 Maruzen Petrochemical Co., Ltd. Process for production of N-vinyllactam
EP0982293A1 (en) * 1998-08-14 2000-03-01 Basf Aktiengesellschaft Process for the preparation of imines and enamines, and possibly their further hydrogenation into amines
WO2001090066A3 (en) * 2000-05-26 2002-08-01 Basf Ag Method for obtaining pure n-vinyl pyrrolidone
US6462201B1 (en) * 1998-12-29 2002-10-08 Isp Investments Inc. Process for the production of N-vinyl-2-pyrrolidone by vinylation
WO2009071479A1 (en) * 2007-12-07 2009-06-11 Basf Se Method for producing n-vinyl pyrrolidone from lactone-free pyrrolidone
EP2070912A1 (en) * 2007-12-11 2009-06-17 Basf Se Method for the vinylation of amides
CN102503880A (en) * 2011-10-18 2012-06-20 华诺森（武汉）生物医药技术有限公司 Method for purifying N-vinyl compound
CN101391974B (en) * 2008-11-03 2012-07-04 厦门大学 Process for production of N-vinyl pyrrolidone
CN103003238A (en) * 2010-05-19 2013-03-27 生物琥珀酸有限公司 Processes for the productions of pyrrolidones
EP2835365A1 (en) 2013-08-06 2015-02-11 S.P.C.M. Sa A process to produce N-ethenyl-N-alkyl-alkylamides
CN117654619A (en) * 2024-01-31 2024-03-08 山东惟普控股有限公司 Catalyst for synthesizing N-vinyl pyrrolidone and preparation method thereof

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Publication number Priority date Publication date Assignee Title
IL100360A (en) * 1990-12-17 1998-08-16 Merrell Dow Pharma Pyrrolidinone derivatives useful as intermediates for the production of (s) vinyl and allenyl gaba
DE4333237A1 (en) * 1993-09-30 1995-04-06 Basf Ag Process for the preparation of N-vinyl compounds

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US3249625A (en) * 1961-09-21 1966-05-03 Hoechst Ag Process for preparing nu-vinyl pyrrolidone-2

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US2317804A (en) * 1938-12-31 1943-04-27 Reppe Walter N-vinyl lactams
US3249625A (en) * 1961-09-21 1966-05-03 Hoechst Ag Process for preparing nu-vinyl pyrrolidone-2

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5329021A (en) * 1993-02-04 1994-07-12 Isp Investments Inc. Process for the production of pure vinyl pyrrolidone
WO1994018166A1 (en) * 1993-02-04 1994-08-18 Isp Investments Inc. Process for the production of pure vinyl pyrrolidone
US5670639A (en) * 1995-03-15 1997-09-23 Basf Aktiengesellschaft Preparation of n-vinyllactams
US5710284A (en) * 1995-10-02 1998-01-20 Basf Aktiengesellschaft Purification of N-vinylpyrrolidone by crystallization
US5665889A (en) * 1996-01-22 1997-09-09 Industrial Technology Research Institute Method for the production of N-vinyl-2-pyrrolidone by vinylation
US5945544A (en) * 1997-04-09 1999-08-31 Maruzen Petrochemical Co., Ltd. Process for production of N-vinyllactam
EP0982293A1 (en) * 1998-08-14 2000-03-01 Basf Aktiengesellschaft Process for the preparation of imines and enamines, and possibly their further hydrogenation into amines
US6462201B1 (en) * 1998-12-29 2002-10-08 Isp Investments Inc. Process for the production of N-vinyl-2-pyrrolidone by vinylation
DE19983849B3 (en) 1998-12-29 2018-05-30 Isp Investments Inc. Process for the preparation of N-vinyl lactams by vinylation
WO2001090066A3 (en) * 2000-05-26 2002-08-01 Basf Ag Method for obtaining pure n-vinyl pyrrolidone
US20030166947A1 (en) * 2000-05-26 2003-09-04 Bernd Eck Method for obtaining pure n-vinyl pyrrolidone
US6703511B2 (en) 2000-05-26 2004-03-09 Basf Aktiengesellschaft Method for obtaining pure n-vinyl pyrrolidone
WO2009071479A1 (en) * 2007-12-07 2009-06-11 Basf Se Method for producing n-vinyl pyrrolidone from lactone-free pyrrolidone
US20110034706A1 (en) * 2007-12-07 2011-02-10 Basf Se Process for preparing n-vinylpyrrolidone from lactone-free pyrrolidone
EP2070912A1 (en) * 2007-12-11 2009-06-17 Basf Se Method for the vinylation of amides
US20100249434A1 (en) * 2007-12-11 2010-09-30 Base Se Method for the vinylation of amides
US9249094B2 (en) 2007-12-11 2016-02-02 Basf Se Method for the vinylation of amides
WO2009074534A1 (en) * 2007-12-11 2009-06-18 Basf Se Method for the vinylation of amides
CN101391974B (en) * 2008-11-03 2012-07-04 厦门大学 Process for production of N-vinyl pyrrolidone
CN103003238A (en) * 2010-05-19 2013-03-27 生物琥珀酸有限公司 Processes for the productions of pyrrolidones
CN102503880A (en) * 2011-10-18 2012-06-20 华诺森（武汉）生物医药技术有限公司 Method for purifying N-vinyl compound
EP2835365A1 (en) 2013-08-06 2015-02-11 S.P.C.M. Sa A process to produce N-ethenyl-N-alkyl-alkylamides
CN117654619A (en) * 2024-01-31 2024-03-08 山东惟普控股有限公司 Catalyst for synthesizing N-vinyl pyrrolidone and preparation method thereof
CN117654619B (en) * 2024-01-31 2024-04-02 山东惟普控股有限公司 Catalyst for synthesizing N-vinyl pyrrolidone and preparation method thereof

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EP0408652A1 (en) 1991-01-23
WO1989009210A1 (en) 1989-10-05
AU3443189A (en) 1989-10-16
KR900700451A (en) 1990-08-13
EP0408652A4 (en) 1991-09-11
JPH04501252A (en) 1992-03-05

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